XLi3N2 compounds and their hydrides as hydrogen storage materials

ABSTRACT

State-of-the-art electronic structure calculations provide the likelihood of the availability of ScLi 3 N 2 , TiLi 3 N 2 , VLi 3 N 2 , CrLi 3 N 2 , MnLi 3 N 2 , CoLi 3 N 2 , NiLi 3 N 2 , CuLi 3 N 2 , and ZnLi 3 N 2  as compounds for reaction with hydrogen under suitable conditions. Reaction with hydrogen is likely to form stable hydrides of the family ScLi 3 N 2 H n , TiLi 3 N 2 H n , VLi 3 N 2 H n , CrLi 3 N 2 H n , MnLi 3 N 2 H n , FeLi 3 N 2 H n  CoLi 3 N 2 H n , NiLi 3 N 2 H n , CuLi 3 N 2 H n , and ZnLi 3 N 2 H n , where n is an integer in the range of 1-4. These materials offer utility for hydrogen storage systems

TECHNICAL FIELD

This invention pertains to compounds useful for solid-state storage of hydrogen. More specifically, this invention pertains to a family of new compounds, XLi₃N₂, which form hydrides, XLi₃N₂H_(n), where X is a 3d transition metal.

BACKGROUND OF THE INVENTION

Considerable development effort is currently being expended on the development of hydrogen and oxygen consuming fuel cells, and there is also interest in hydrogen burning engines. Such power systems require means for storage of hydrogen fuel which hold hydrogen in a safe form at ambient conditions and which are capable of quickly receiving and releasing hydrogen. In the case of automotive vehicles, fuel storage is required to be on-board the vehicle, and storage of hydrogen gas at high pressure is generally not acceptable for such applications.

These requirements have led to the study and development of solid-state compounds for temporary storage of hydrogen, often as hydrides. For example, sodium alanate, NaAlH₄, can be heated to release hydrogen gas, and a mixture of lithium amide, LiNH₂, and lithium hydride, LiH, can be heated and reacted with the same effect. Despite such progress, however, no known solid-state system currently satisfies targets for on-board vehicular hydrogen storage.

SUMMARY OF THE INVENTION

FeLi₃N₂ is prepared by reaction of Li₃N melt with elemental iron in a nitrogen atmosphere. It crystallizes in the body-centered Ibam structure (space group 72). However, other compounds like XLi₃N₂, where X is any of the 3d transition elements (Sc—Zn) other than iron, are unknown. These other ternary nitride compounds, having the same stoichiometry as FeLi₃N₂, are of interest as hydrogen storage materials where the ternary nitride takes up hydrogen as XLi₃N₂H_(n).

State-of-the-art computational electronic structure methods, using FeLi₃N₂ as the template compound, indicate that these ternary nitrides, XLi₃N₂, are thermodynamically stable. Accordingly, this invention demonstrates the credible likelihood that each of ScLi₃N₂, TiLi₃N₂, VLi₃N₂, CrLi₃N₂, MnLi₃N₂, CoLi₃N₂, NiLi₃N₂, CuLi₃N₂, and ZnLi₃N₂ can be prepared as new materials for storage of hydrogen. The computational methods also show thermodynamic stability of the hydrides ScLi₃N₂H_(n), TiLi₃N₂H_(n), VLi₃N₂H_(n), CrLi₃N₂H_(n), MnLi₃N₂H_(n), FeLi₃N₂H_(n), CoLi₃N₂H_(n), NiLi₃NH_(n), CuLi₃N₂H_(n), and ZnLi₃N₂H_(n). Accordingly, this invention also provides the likelihood of a hydrogen storage compound for each of the specified ternary nitride compositional formulas.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the experimentally determined structure of FeLi₃N₂ that is the template for computational electronic structure methods showing the thermodynamic stability of other isostructural ternary nitride compounds, XLi₃N₂. In this figure, the large dark-filled circles represent the positions of nitrogen atoms, the speckled circles represent the positions of iron atoms, and the small unfilled circles represent positions of lithium atoms.

FIG. 2 illustrates the calculated structure of FeLi₃N₂H₂ with H atoms occupying the 8j sites in the Ibam structure; it is the most thermodynamically stable hydride of FeLi₃N₂ identified with the computational methodology used here. In this figure, the large dark filled circles represent the positions of nitrogen atoms, the speckled circles represent the positions of iron atoms, the small unfilled circles represent positions of lithium atoms, and the small dark filled circles represent positions of hydrogen atoms.

DESCRIPTION OF PREFERRED EMBODIMENTS

State-of-the-art computational electronic structure methods implementing density functional theory (DFT) have been employed with substantial success to model hydride properties, including the crucial enthalpies of formation. That success encourages the development of strategies for harnessing the calculational tools to guide the discovery of novel hydrides. The approach in this case is to choose a compound having a known crystal structure and calculate enthalpies of formation for isostructural, hypothetical compounds constructed by elemental replacements and the addition of hydrogen to the original lattice.

In this work FeLi₃N₂ is selected as the template compound, and the formation of isostructural XLi₃N₂ phases and their XLi₃N₂H_(n) hydrides with X any of the 3d transition elements (Sc—Zn) or boron, aluminum, or gallium is considered. Searching for hydrides comprising a 3d element such as Ni or Fe to facilitate H₂ dissociation and lighter elements such as Li to enhance the gravimetric hydrogen density is the strategy. This strategy is believed to be realistic because two of the most comprehensively investigated hydrides have Ni as a component: LaNi₅H₇ and Mg₂NiH₄; the former has excellent H₂ sorption characteristics but is only 1.4 mass % H, while the latter requires heating to at least 250° C. for hydrogen liberation. Compounds having the XLi₃N₂ stoichiometry are only known for X═B, Fe, Al, and Ga, and the only known hydrides are those recently identified in the B—Li—N—H system.

Crystal Structure of FeLi₃N₂

FeLi₃N₂ crystallizes in the body-centered orthorhombic Ibam structure (space group No. 72). The conventional unit cell, illustrated in FIG. 1, contains four FeLi₃N₂ formula units (f.u.). The space group allows eleven distinct crystallographic sites; the 4a, 4b, 4c, 4d, and 8e positions are fixed by symmetry, while the 8f, 8g, 8h, 8i, 8j, and 16k sites have variable coordinates and thus can be multiply occupied. In FeLi₃N₂, iron and nitrogen ions occupy the 4a and 8j sites, respectively, and the lithium ions fill the 4b and 8g sites. FeLi₃N₂ contains infinite chains of edge-sharing FeN₄ tetrahedra along the c-direction. These chains are isoelectronic to the SiS₂ one-dimensional macromolecule and form nearly hexagonal arrays linked by sharing common edges with LiN₄ tetrahedra. Two of these tetrahedra are highlighted with speckling in FIG. 1.

Calculation Procedures

Electronic total energies E were computed for the primitive cells (containing two formula units, f.u.) with the Vienna ab initio simulation package (VASP), which implements DFT using a plane wave basis set. Projector-augmented wave potentials were employed for the elemental constituents, and a generalized gradient approximation (GGA) was used for the exchange-correlation energy functional 1,. Paramagnetic calculations were performed for all materials except those containing Fe, Co, and Ni, for which spin-polarized calculations were done to assess the possibility of magnetic states. An interpolation formula was used for the correlation component of μ_(xc) in the spin-polarized cases. For all the XLi₃N₂ and XLi₃N₂H, compounds a plane wave cutoff energy of 900 eV was imposed and (6 6 6) Monkhorst-type k-point grids having 45 points in the irreducible Brillouin zone were employed. In each case at least two simultaneous relaxations of the lattice constants and nuclear coordinates not fixed by the space group were carried out. The electronic total energies and forces were converged to 10⁻⁶ eV/cell and 10⁻⁴ eV/Å, respectively. Calculations for the H₂, N₂ molecules and the elemental metals Li, X were performed with the same computational machinery to the same levels of precision.

Enthalpies of formation, ΔH, were obtained from total energy differences: ΔH(XLi₃N₂)=E(XLi₃N₂)−E(X)−3E(Li)−E(N₂)   (1) for the parent compounds, and ΔH(XLi₃N₂H_(n))=(2/n) [E(XLi₃N₂H_(n))−E(X)−3E(Li)−E(N₂)−(n/2)E(H₂)]  (2) for the hydrides, where n is the number of H atoms in a given configuration. Each ΔH, specified per XLi₃N₂ formula unit (f.u.) in equation (1) and per H₂ molecule in equation (2), is the standard enthalpy of formation at zero temperature in the absence of zero point energy contributions. A negative ΔH indicates stability of the material relative to its elemental solid and molecular constituents. Results of Calculations XLi₃N₂ Parent Compounds

Table I lists ΔH(XLi₃N₂) calculated according to equation (1) for the 3d transition elements X═Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, as well as for X═B, Al, and Ga. The compounds are in the Ibam structure of FeLi₃N₂. All ΔH values are in kJ/mole formula unit. Only FeLi₃N₂, BLi₃N₂, AlLi₃N₂, and GaLi₃N₂ are known to exist. TABLE 1 ΔH(XLi₃N₂) Compound (kJ/mole f.u.) ScLi₃N₂ −458 TiLi₃N₂ −446 VLi₃N₂ −384 CrLi₃N₂ −333 MnLi₃N₂ −295 FeLi₃N₂ −246 CoLi₃N₂ −184 NiLi₃N₂ −119 CuLi₃N₂ −28 ZnLi₃N₂ −117 BLi₃N₂ −379 AlLi₃N₂ −482 GaLi₃N₂ −285

In each case ΔH<0, suggesting that all the compounds may form. This is certainly correct for FeLi₃N₂, the prototype. Encouragingly, it is also true for BLi₃N₂, AlLi₃N₂, and GaLi₃N₂. BLi₃N₂ forms in at least three structures all distinct from Ibam: (i) a tetragonal P4₂2₁2 low-temperature phase, (ii) a monoclinic P2₁/c phase often observed at high temperatures, and (iii) a body-centered tetragonal I4₁/amd phase only recently established. AlLi₃N₂ and GaLi₃N₂ are known to form in the body-centered cubic Ia3 structure. All the other compounds in Table I are unknown. Although the results in the table indicate compound existence, the BLi₃N₂, AlLi₃N₂, and GaLi₃N₂ examples emphasize the very likely possibility that the actual XLi₃N₂ crystal structure for X other than Fe could well differ from the Ibam FeLi₃N₂ template on which the calculations are based. Furthermore, ΔH in Table I sets an upper bound on the actual ΔH. If an XLi₃N₂ compound exists and its structure differs from that of FeLi₃N₂, then its ΔH will be more negative than the value in Table I. BLi₃N₂ also illustrates this point. The enthalpies of formation of the three known structures, also calculated via Eq. (1), are all ˜−500 kJ/f.u., substantially lower than ΔH=−379 kJ/f.u. in Table I for BLi₃N₂ in the Ibam structure.

Plots of the electronic density of states (DoS) were calculated for each XLi₃N₂ compound. All the materials in Table I are metals with the exception of ScLi₃N₂ and BLi₃N₂, which are insulators. Analogous computations for the three known BLi₃N₂ phases indicate that all are also insulators with a gap of ˜3 eV separating the valence and conduction bands.

FeLi₃N₂, CoLi₃N₂, and NiLi₃N₂ were found to have net magnetic moments of 0.97, 0.17, and 0.19 gB/f.u.

XLi₃N₂H_(n) Hydrides

Since the fixed-coordinate 4a and 4b sites in the Ibam structure are occupied by X and Li, respectively, the 4c, 4d, 8e, 8f, 8g, 8h, 8i, and 16k sites, and combinations of them, are available for occupation by hydrogen. All these sites other than the 4c, 4d, and 8e can be multiply occupied, so that in principle an infinite number of hydrogen configurations are possible. For each element X calculations of ΔH(XLi₃N₂H_(n)) as defined by Eq. (2) were performed to assess whether stable [ΔH(XLi₃N₂H_(n))<0] hydride configurations exist and to find the most stable configuration, that for which ΔH(XLi₃N₂H_(n)) is a minimum. According to the van't Hoff relation ln p/p ₀=ΔH/RT−ΔS/R,   (3) where ΔS is the entropy of formation and R the gas constant, the configuration having the most negative ΔH is that which is stable at the lowest H₂ pressure p.

Calculations were carried out for hydrogen occupying each of the possible individual sites and for the 4c4d, 4d8j, 8j₁8j₂, 4d8j₁8j₂, 8j16k, and 16k₁16k₂ combinations. This spectrum of choices was sufficiently comprehensive to ensure that the configuration having the minimum ΔH was identified for each XLi₃N₂H_(n). Several negative ΔH values were found for every X, suggesting the possibility of hydride formation in each case. The most stable hydrogen configuration varies through the XLi₃N₂H_(n) series. The 4d sites provide the greatest stability for X═Sc, Ti; the 8j₁8j₂ combination for X═V, Cr; the 8j sites for X═Mn, Fe, Co, Ni, Cu; and the 16k sites in the Zn hydride. The most unstable arrangements are those for hydrogen in the 8f, 8g, 8h, and 8i sites. It appears likely that hydrogen filling of these sites destabilizes the interaction between the Li ions on the 4b and 8g sites and the N ions on the 8j sites.

No XLi₃N₂H_(n) hydrides are known for X═Sc—Zn but, as for the parent compounds, the case of boron provides encouragement that at least some may form. The calculations for BLi₃N₂H_(n) in the Ibam structure reveal BLi₃N₂H₄ with hydrogen occupying 8j₁8j₂ sites as the most stable; each conventional cell contains four BLi₃N₂H₄ formula units. This result is in qualitative accord with the fact that BLi₄N₃H₁₀ and other B—Li—N—H hydrides have indeed been synthesized.

Table II summarizes the minimum ΔH results from the calculations and includes the hydrogen mass percentage for each hypothetical hydride. The crystallographic sites occupied by hydrogen are indicated in parentheses in the first column. All ΔH values in kJ/mole H₂. Only B—Li—N—H hydrides are known to exist. If any of these were to form in a different crystal structure or with an alternate stoichiometry the hydrogen content could certainly change. In particular, the 6.3 mass % value for BLi₃N₂H₄ in Table II underestimates the 11.1 H mass % for the actual BLi₄N₃H₁₀ hydride. TABLE 2 XLi₃N₂ hydride (H configuration in ΔH(XLi₃N₂) conventional cell) (kJ/mole H₂) mass % H ScLi₃N₂H (4d) −439 1.1 TiLi₃N₂H (4d) −331 1.0 VLi₃N₂H₄ (8j₁8j₂) −198 3.9 CrLi₃N₂H₄ (8j₁8j₂) −155 3.8 MnLi₃N₂H₂ (8j) −128 1.9 FeLi₃N₂H₂ (8j) −124 1.9 CoLi₃N₂H₂ (8j) −144 1.8 NiLi₃N₂H₂ (8j) −143 1.8 CuLi₃N₂H₂ (8j) −178 1.8 ZnLi₃N₂H₄ (16k) −148 3.4 BLi₃N₂H₄ (8j₁8j₂) −228 6.3

To determine the effect of hydriding on the electronic structure the electronic densities of states (DoS) for the hydrides characterized by the minimum AH were calculated together with the DoS for the parents. In each case hydrogen-derived bands appear below the bottom of the valence bands of the parent, similar to the behavior of LaNi₅ on hydriding. From the DoS at the Fermi energy ε_(F) it became apparent that the X═Sc, Ti, V, Cr, Fe, Ni, and Zn hydrides are metals. NiLi₃N₂H₂ (8j) [occupied hydrogen sites in parentheses] is in fact a half-metal since the majority (↑) spin DoS is zero at ε_(F) while there is substantial minority (↓) spin DoS at the Fermi level. The X═Mn, Co, Cu, and B hydrides are all insulators (zero DoS and gaps at ε_(F)).

Most of the XLi₃N₂ parents are metals and remain metallic on hydrogen uptake, and BLi₃N₂ and its BLi₃N₂H₄ (8j₁8j₂) hydride are both insulators. The X═Sc, Mn, Co, Cu, and Ni materials, however, feature three types of intriguing electronic transitions on hydriding to the minimum ΔH configuration. First, ScLi₃N₂ is an insulator, but its ScLi₃N₂H (4d) hydride is a metal. Second, MnLi₃N₂, CoLi₃N₂, and CuLi₃N₂ are metals, while their corresponding MnLi₃N₂H₂ (8j), CoLi₃N₂H₂ (8j), and CuLi₃N₂H₂ (8j) hydrides are insulators. Third, NiLi₃N₂ is metallic in both spin bands, but its NiLi₃N₂H₂ (8j) hydride is predicted to be a half-metal. Were these materials to form, such transitions might serve as the bases for hydrogen sensor applications.

These state-of-the-art electronic structure calculations demonstrate the credible likelihood of the availability of ScLi₃N₂, TiLi₃N₂, VLi₃N₂, CrLi₃N₂, MnLi₃N₂, CoLi₃N₂, NiLi₃N₂, CuLi₃N₂, and ZnLi₃N₂ as compounds for reaction with hydrogen under suitable conditions. Reaction with hydrogen should form stable hydrides of the family ScLi₃N₂H_(n), TiLi₃N₂H_(n), VLi₃N₂H_(n), CrLi₃N₂H_(n), MnLi₃N₂H_(n), CoLi₃N₂H_(n), NiLi₃N₂H_(n), CuLi₃N₂H_(n), and ZnLi₃N₂H_(n), where n is an integer in the range of 1-4.

The above-described synthesis of FeLi₃N₂, adapted for the properties of the specific other elements of the 3d transition metal group, provides a basis for the synthesis of the parent compounds. 

1. Any one or more of the ternary nitrides of the following compositional formulas; ScLi₃N₂, TiLi₃N₂, VLi₃N₂, CrLi₃N₂, MnLi₃N₂, CoLi₃N₂, NiLi₃N₂, CuLi₃N₂, and ZnLi₃N₂.
 2. Any one or more of the ternary nitrides as recited in claim 1 for the storage of hydrogen as a hydride of the ternary nitride.
 3. Any one or more of the hydrides of ternary nitrides of the 3d transition metals having the following compositional formulas; ScLi₃N₂H_(n), TiLi₃N₂H_(n), VLi₃N₂H_(n), CrLi₃N₂H_(n), MnLi₃N₂H_(n), FeLi₃N₂H_(n), CoLi₃N₂H_(n), NiLi₃N₂H_(n), CuLi₃N₂H_(n), and ZnLi₃N₂H_(n), where n is an integer having a value of from 1 to
 4. 4. Any one or more of the hydrides of ternary nitrides of the 3d transition metals as recited in claim 3 having the following compositional formulas; ScLi₃N₂H, TiLi₃N₂H, VLi₃N₂H₄, CrLi₃N₂H₄, MnLi₃N₂H₂, FeLi₃N₂H₂ CoLi₃N₂H₂, NiLi₃N₂H₂, CuLi₃N₂H₂, and ZnLi₃N₂H₄.
 5. A hydride of a ternary nitride of a 3d transition metal as recited in claim 3 when used for hydrogen storage.
 6. A hydride of a ternary nitride of a 3d transition metal as recited in claim 4 when used for hydrogen storage. 